CN111122542A - Method for measuring sulfide in water by using surface enhanced Raman spectroscopy - Google Patents
Method for measuring sulfide in water by using surface enhanced Raman spectroscopy Download PDFInfo
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- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
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Abstract
The invention discloses a method for measuring sulfide in water by utilizing a surface enhanced Raman spectroscopy technology, which comprises the following steps: the sulfide reacts with N, N-dimethyl-p-phenylenediamine and Fe under acidic condition3+The reaction produces methylene blue, which can be measured using surface enhanced raman spectroscopy. The method has the advantages of simple and convenient operation, high sensitivity, detection limit of 3nmol/L, less reagent consumption, environmental friendliness, good selectivity, high precision and accuracy, and suitability for measuring sulfide in surface water and sewage.
Description
Technical Field
The invention belongs to the technical field of environmental monitoring, and particularly relates to a method for measuring sulfide in water by using a surface enhanced Raman spectroscopy technology.
Background
Sulfide is one of important indexes indicating environmental water body pollution, and mainly comes from the discharge of sewage and wastewater in human production and life and metabolites of sulfate reducing bacteria in nature. Environment(s)The form of sulfide in water body is influenced by pH, and when pH is greater than or equal to 8, the sulfide is S2-Exists in the form of (1); at pH < 7, the sulfide morphology will be converted to more toxic HS-and H2S, even under the condition of low concentration, the health and stability of a water ecosystem can be damaged, such as causing oxygen deficiency and stink of water, inhibiting the growth of plant roots, harming the growth and survival of fishes, and the like. In addition, hydrogen sulfide dissipated from the water body can react with human cytochrome, oxidase and disulfide bonds in the substances to block the oxidation process of cells, so that oxygen deficiency of the cells is caused, and the life of a human is endangered.
At present, methods for measuring sulfide in environmental water mainly include methylene blue spectrophotometry, fluorescence, chromatography and the like. However, the above methods still have their respective limitations: the sensitivity of the methylene blue spectrophotometry is low, the detection limit is generally more than 0.16 mu mol/L, and the sample needs to be enriched to meet the requirement of trace analysis; the fluorescence method has poor selectivity and is easily interfered by natural fluorescent substances and organic sulfides; chromatography is cumbersome, time consuming and requires large instruments. Therefore, it is necessary to search for a simple, rapid, economical, efficient and highly sensitive method for detecting sulfide.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for measuring sulfide in water by using a surface enhanced Raman spectroscopy technology.
The principle of the invention is as follows: the sulfide reacts with N, N-dimethyl-p-phenylenediamine and Fe under acidic condition3+The reaction produces methylene blue, which can be measured using surface enhanced raman spectroscopy.
The technical scheme of the invention is as follows:
a method for measuring sulfide in water by using a surface enhanced Raman spectroscopy technology comprises the following steps:
(1) filtering the collected water sample by using a filter membrane of 0.4-0.5 mu m, and adding a zinc acetate solution and a sodium hydroxide solution to fix sulfides in the water sample to obtain a solution to be detected with the pH value of more than 10;
(2) accurately obtaining a proper amount of the liquid to be detected, centrifuging for 5-10min, removing supernatant, and adding ultrapure water to constant volume to the original volume;
(3) sequentially adding an N, N-dimethyl-p-phenylenediamine solution and an iron chloride solution into the liquid obtained in the step (2), and fully and uniformly mixing for reaction to obtain a reaction liquid; the solvent of the N, N-dimethyl-p-phenylenediamine solution and the ferric chloride solution is a hydrochloric acid solution or a sulfuric acid solution;
(4) and (3) sequentially adding an inorganic salt agglomerating agent and an activity enhancing substrate into a proper amount of the reaction solution, quickly and uniformly mixing, and detecting the concentration of the methylene blue by using a Raman spectrometer.
In a preferred embodiment of the invention, the concentration of the sodium hydroxide solution is between 0.1 and 10.0 mol/L.
In a preferred embodiment of the present invention, the concentration of the zinc acetate solution is 0.5 to 2.0 mol/L.
In a preferred embodiment of the present invention, the concentration of the N, N-dimethyl-p-phenylenediamine solution is 10-6-10-4mol/L, concentration of ferric chloride solution is 10-5-10-3mol/L。
In a preferred embodiment of the present invention, the concentration of the hydrochloric acid or sulfuric acid in the N, N-dimethyl-p-phenylenediamine solution and the ferric chloride solution is 0.01 to 3.0 mol/L.
In a preferred embodiment of the present invention, the time of the reaction in the step (3) is at least 30 min.
In a preferred embodiment of the present invention, the inorganic salt agglomerating agent includes sodium chloride, potassium chloride, magnesium chloride, sodium sulfate, potassium sulfate, magnesium sulfate, sodium bromide, and potassium bromide.
In a preferred embodiment of the present invention, the activity enhancing substrate is a gold nanoparticle sol or a silver nanoparticle sol.
Further preferably, the rotation speed of the centrifugation is 1000-.
More preferably, in the step (4), the excitation wavelength detected by the raman spectrometer is 785nm, the integration time is 1 to 5s, and the number of integration times is 5.
The invention has the beneficial effects that:
1. the method is simple and convenient to operate, high in sensitivity and detection limit reaching 3 nmol/L.
2. The invention has the advantages of low reagent consumption and environmental protection.
3. The method has the advantages of good selectivity, high precision and high accuracy, and can be suitable for measuring the sulfide in surface water and sewage.
Drawings
FIG. 1 is a surface enhanced Raman spectrum of lake water in which the sulfide content is measured in example 1 of the present invention.
FIG. 2 is a surface enhanced Raman spectrum of the sulfide content in the wastewater measured in example 2 of the present invention.
Detailed Description
The technical solution of the present invention will be further illustrated and described below with reference to the accompanying drawings by means of specific embodiments.
Example 1
(1) Filtering the collected lake water sample by using a 0.45 mu m filter membrane, adding a zinc acetate solution and a sodium hydroxide solution to fix sulfides in the lake water sample to obtain a solution to be detected with the pH value of more than 10, and hermetically storing the solution to be detected at the temperature of 4 ℃; wherein, 1mL of zinc acetate solution with the concentration of 1.0mol/L is added into each 100mL of water sample, and 1.0mol/L of sodium hydroxide solution is used for adjusting the pH value to be more than 10;
(2) accurately obtaining 10mL of the solution to be detected, placing the solution into a centrifuge tube, centrifuging the solution at 3500rpm for 5min, removing supernatant, and then using ultrapure water to fix the volume to 10 mL;
(3) 2.5mL of 10 concentration solution was added to the liquid obtained in step (2)-5mol/L of N, N-dimethyl-p-phenylenediamine solution and 2.5mL of 10-concentration solution-4Fully and uniformly mixing the mol/L ferric chloride solution, and reacting for 60min to obtain a reaction solution; the solvent of the N, N-dimethyl-p-phenylenediamine solution and the ferric chloride solution is hydrochloric acid solution with the concentration of 0.3 mol/L;
(4) accurately obtaining 200 mu L of the reaction solution, sequentially adding 50 mu L of sodium sulfate solution with the concentration of 1.2mol/L and 8 mu L of gold nanoparticle sol (the average particle size is 55nm), quickly mixing uniformly, and detecting the concentration of methylene blue by using a Raman spectrometer, wherein the detected laser wavelength is 785nm, the integration time is 2.5s, the cumulative frequency is 5 times, and the detection results are shown in figure 1 and table 1.
TABLE 1
The preparation method of the gold nano-ion sol comprises the following steps: weighing 50mL of chloroauric acid solution with the concentration of 6.5% in a 100mL double-mouth round-bottom flask, continuously stirring the solution at the rotating speed of 1500rpm, heating the solution to boiling for 3-5min, quickly adding 3.3mL of trisodium citrate solution with the concentration of 1%, gradually changing the solution from golden yellow to colorless to wine red, keeping boiling for 15min, stopping heating, and continuously stirring and cooling the solution to room temperature. The gold nanoparticle sol is prepared and stored at 4 ℃ for later use.
The ultrapure water used in the embodiment is deoxygenated water blown off by nitrogen or helium.
Example 2
(1) Filtering the collected sewage sample by using a 0.45 mu m filter membrane, adding a zinc acetate solution and a sodium hydroxide solution to fix sulfides in the sewage sample to obtain a solution to be detected with the pH value of more than 10, and hermetically storing the solution to be detected at the temperature of 4 ℃; wherein, 1mL of zinc acetate solution with the concentration of 1.0mol/L is added into each 100mL of water sample, and 1.0mol/L of sodium hydroxide solution is used for adjusting the pH value to be more than 10;
(2) accurately obtaining 10mL of the solution to be detected, placing the solution into a centrifuge tube, centrifuging the solution at 3500rpm for 5min, removing supernatant, and then using ultrapure water to fix the volume to 10 mL;
(3) 2.5mL of 10 concentration solution was added to the liquid obtained in step (2)-5mol/L of N, N-dimethyl-p-phenylenediamine solution and 2.5mL of 10-concentration solution-4Fully and uniformly mixing the mol/L ferric chloride solution, and reacting for 60min to obtain a reaction solution; the solvent of the N, N-dimethyl-p-phenylenediamine solution and the ferric chloride solution is hydrochloric acid solution with the concentration of 0.3 mol/L;
(4) accurately obtaining 200 mu L of the reaction solution, sequentially adding 50 mu L of sodium sulfate solution with the concentration of 1.2mol/L and 8 mu L of gold nanoparticle sol (the average particle size is 55nm), quickly mixing uniformly, and detecting the concentration of methylene blue by using a Raman spectrometer, wherein the detected laser wavelength is 785nm, the integration time is 2.5s, the cumulative frequency is 5 times, and the detection results are shown in figure 2 and table 2.
TABLE 2
The preparation method of the gold nano-ion sol comprises the following steps: weighing 50mL of chloroauric acid solution with the concentration of 6.5% in a 100mL double-mouth round-bottom flask, continuously stirring the solution at the rotating speed of 1500rpm, heating the solution to boiling for 3-5min, quickly adding 3.3mL of trisodium citrate solution with the concentration of 1%, gradually changing the solution from golden yellow to colorless to wine red, keeping boiling for 15min, stopping heating, and continuously stirring and cooling the solution to room temperature. The gold nanoparticle sol is prepared and stored at 4 ℃ for later use.
The ultrapure water used in the embodiment is deoxygenated water blown off by nitrogen or helium.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.
Claims (10)
1. A method for measuring sulfide in water by using a surface enhanced Raman spectroscopy technology is characterized by comprising the following steps: the method comprises the following steps:
(1) filtering the collected water sample by using a filter membrane of 0.4-0.5 mu m, and adding a zinc acetate solution and a sodium hydroxide solution to fix sulfides in the water sample to obtain a solution to be detected with the pH value of more than 10;
(2) accurately obtaining a proper amount of the liquid to be detected, centrifuging for 5-10min, removing supernatant, and adding ultrapure water to constant volume to the original volume;
(3) sequentially adding an N, N-dimethyl-p-phenylenediamine solution and an iron chloride solution into the liquid obtained in the step (2), and fully and uniformly mixing for reaction to obtain a reaction liquid; the solvent of the N, N-dimethyl-p-phenylenediamine solution and the ferric chloride solution is a hydrochloric acid solution or a sulfuric acid solution;
(4) and (3) sequentially adding an inorganic salt agglomerating agent and an activity enhancing substrate into a proper amount of the reaction solution, quickly and uniformly mixing, and detecting the concentration of the methylene blue by using a Raman spectrometer.
2. The method of claim 1, wherein: the concentration of the sodium hydroxide solution is 0.1-10.0 mol/L.
3. The method of claim 1, wherein: the concentration of the zinc acetate solution is 0.5-2.0 mol/L.
4. The method of claim 1, wherein: the concentration of the N, N-dimethyl-p-phenylenediamine solution is 10-6-10-4mol/L, concentration of ferric chloride solution is 10-5-10-3mol/L。
5. The method of claim 1, wherein: the concentration of the hydrochloric acid or the sulfuric acid in the N, N-dimethyl-p-phenylenediamine solution and the ferric chloride solution is 0.01-3.0 mol/L.
6. The method of claim 1, wherein: the rotation speed of the centrifugation in the step (2) is 1000-.
7. The method of claim 1, wherein: the reaction time in the step (3) is at least 30 min.
8. The method of claim 1, wherein: the inorganic salt agglomerating agent comprises sodium chloride, potassium chloride, magnesium chloride, sodium sulfate, potassium sulfate, magnesium sulfate, sodium bromide and potassium bromide.
9. The method of claim 1, wherein: the activity enhancing substrate is gold nanoparticle sol or silver nanoparticle sol.
10. The method of claim 1, wherein: in the step (4), the excitation wavelength detected by the Raman spectrometer is 785nm, the integration time is 1-5s, and the accumulation frequency is 5 times.
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| WO2014178006A2 (en) * | 2013-05-01 | 2014-11-06 | Indian Institute Of Technology Madras | Coated mesoflowers for molecular detection and smart barcode materials |
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Application publication date: 20200508 |